WO2017140580A1

WO2017140580A1 - Preactivated catalyst component for the polymerization of olefins

Info

Publication number: WO2017140580A1
Application number: PCT/EP2017/052953
Authority: WO
Inventors: Martin Schneider
Original assignee: Basell Poliolefine GmbH
Priority date: 2016-02-15
Filing date: 2017-02-10
Publication date: 2017-08-24
Also published as: EP3416990A1; US20190177446A1; ES2812813T3; CN108602912B; CN108602912A; WO2017140580A8; EP3416990B1; BR112018015611A2

Abstract

A process for the manufacture of pre-activated or pre-polymerized catalysts for the polymerization of olefins is disclosed. In particular, the present disclosure relates to a process for the preparation of pre-activated or pre-polymerized catalysts comprising a solid catalyst component comprising Ti, Mg, halogen said pre-activated catalyst having reduced release of flammable gases in contact with water.

Description

PREACTIVATED CATALYST COMPONENT FOR THE POLYMERIZATION

OF OLEFINS

FIELD OF THE INVENTION

[0001] The present disclosure relates to a process for the manufacture of pre-activated or pre- polymerized catalysts for the polymerization of olefins. In particular, the present disclosure relates to a process for the preparation of pre-activated or pre-polymerized catalysts comprising a solid catalyst component comprising Ti, Mg, halogen said pre-activated ore prepolymerized catalyst having reduced release of flammable gases in contact with water.

BACKGROUND OF THE INVENTION

[0002] The vast majority of polyolefin manufacture is based on Ziegler and Ziegler-Natta catalysts.

[0003] The said catalysts are obtained by reacting a transition metal compound with an activator, also called co-catalyst, which is constituted by an organoaluminum compound.

[0004] The polymerization activity of such catalysts has been improved by the use of solid catalyst components in which the transition metal compound, usually a titanium halide, is supported, through various techniques, on a magnesium dihalide. In case of stereospecific polymerization of alpha olefins the use of an electron donor compound in the solid catalyst component (internal donor) has been found to increase polymer stereoregularity. Moreover, if additional donors (external donors) are used in polymerization in combination with an Al- alkyl compound, the catalyst stereospecificity is further increased.

[0005] Ziegler and Ziegler-Natta catalysts are used in the preparation of various polymers and copolymers of olefin monomers, such as ethylene, propylene, butene-1 hexene-1 etc, using several polymerization techniques such as liquid (slurry, bulk or solution) and gas-phase polymerization.

[0006] The versatility of this class of catalysts is also demonstrated by the fact that variations in the manufacture recipes are able to impart specific properties to the catalyst.

[0007] Prepolymerization of the catalyst with small quantities of olefinic monomers is carried out in order to enhance the morphological stability of the catalyst and reduce the extent of fragmentation in the initial stages of polymerization. As a result, the regularity of polymer particle shape and the polymer bulk density may be increased.

[0008] US4,302,565 teaches to pre-activate a catalyst precursor by contacting it with an aluminum alkyl compound in a Al/Ti ratio from higher than 0 to 10, specifically from 4 to 8.

The pre-activated catalyst is then used in the polymerization process in combination with an additional amount of aluminum alkyl cocatalyst .

[0009] Both the pre-polymerization and the preactivation of the catalyst may leave on the resulting catalyst active organometallic bonds.

[0010] These bonds may be broken and release flammable gases upon contact with water.

While this problem is relatively of minor impact in the polymerization process due to the presence of scavengers which eliminate the water presents in the reactants, it is of more concern when the catalyst have to be stored and/or shipped.

[0011] Generally speaking, the release of flammable gases is in contact with water is a transportation risk, because in case of a leakage of a catalyst container, flammable or combustible gas compositions can be formed in the presence of water or air humidity.

[0012] In addition to the total amount of gas released, it is also worth noting that the risk becomes higher with the increasing speed of gas development. The combination of these factors leads to certain UN transport classifications which, in some cases, provide for the necessity of transportation approvals by national authorities.

[0013] It is therefore felt the need of a process aimed at reducing or eliminating the tendency of the catalyst to produce flammable gases when in contact with water while, at the same time, not significantly changing the catalyst performances.

SUMMARY OF THE INVENTION

[0014] It is therefore an object of the present disclosure a solid catalyst component comprising the product of a process comprising

[0015] (a) a reaction step carried out at a temperature ranging from 0 to 150°C in which a Mg based compound of formula (MgCl_mX2-_m)'nLB, in which m ranges from 0 to 2, n ranges from 0 to 6, X is, independently R, OR, -OCOR or -OC(0)-OR group, in which R is a Ci-C₂o hydrocarbon group, and LB is a Lewis base, is reacted with a Ti compound, having at least a Ti-Cl bond, in an amount such that the Ti/Mg molar ratio is greater than 0.1 optionally in the presence of an electron donor compound thereby obtaining a catalyst precursor;

[0016] (b) a reaction step in which the product coming from the preceding step is reacted with an organo aluminum compound in such an amount to have a Al/Ti ratio of 0.01 to 50 optionally in the presence of an amount of olefin monomer able to produce from 0.1 to 50gr of polymer per gram of catalyst precursor; optionally followed by one or more washing steps;

[0017] (c) treating the catalyst precursor coming from step (b) with a mono or polychlorinated RZ-CI compound in a R^l/Al ratio from 0.01 to 10 where R¹ is hydrogen or a Q-C20 hydrocarbon group and

[0018] (d) isolating and recovering the solid catalyst component.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The Mg based compound used as a starting compound in the reaction step (a) is preferably selected among a magnesium alcoholate of formula Mg(OR 2 )(OR 3 ) compound, in which R 2 and R 3 are identical or different and are each an alkyl radical having 1 to 10 carbon atoms. R 2 and R 3 are preferably alkyl groups having from 2 to 10 carbon atoms or a radical - (CH₂)_nOR⁴, where R⁴ is a Ci-C4-alkyl radical and n is an integer from 2 to 6. Preferably R and R are C₁-C₂-alkyl radical. Examples of such magnesium alkoxides are: magnesium dimethoxide, magnesium diethoxide, magnesium di-i-propoxide, magnesium di-n-propoxide, magnesium di-n-butoxide, magnesium methoxide ethoxide, magnesium ethoxide n-propoxide, magnesium di(2-methyl-l-pentoxide), magnesium di(2-methyl-l-hexoxide), magnesium dimethyl- 1 -hep toxide), magnesium di(2-ethyl-l-pentoxide), magnesium di(2-ethyl-l -hexoxide), magnesium di(2-ethyl-l-heptoxide), magnesium di(2-propyl-l-heptoxide), magnesium di(2- methoxy-1 -ethoxide), magnesium di(3-methoxy-l-propoxide), magnesium di(4-methoxy-l- butoxide), magnesium di(6-methoxy- 1 -hexoxide), magnesium di(2-ethoxy-l -ethoxide), magnesium di(3-ethoxy-l-propoxide), magnesium di(4-ethoxy-l-butoxide), magnesium di(6- ethoxy-1 -hexoxide), magnesium dipentoxide, magnesium dihex oxide. The use of simple magnesium alkoxides such as magnesium diethoxide, magnesium di-n-propoxide and magnesium di-isobutoxide is preferred. Magnesium diethoxide is especially preferred.

[0020] The magnesium alkoxide can be used as a suspension or as a gel dispersion in a hydrocarbon medium. Use of the magnesium alkoxide as a gel dispersion constitutes a preferred embodiment. The commercially available magnesium alkoxides, in particular Mg(OC₂H₅)₂, may have average particle diameter ranging from 200 to 1200 μιη preferably about 500 to 700 μιη. In one embodiment, its particle size has been reduced before being used in the preparation of the catalyst of the present disclosure. In order to do so, the magnesium alcoholate is suspended in an inert, saturated hydrocarbon thereby creating a hydrocarbon suspension. The suspension can be subject to high shear stress conditions by means of a highspeed disperser (for example Ultra-Turrax or Dispax, IKA-Maschinenbau Janke & Kunkel GmbH) working under inert atmosphere(Ar or N2). Preferably, the shear stress is applied until a gel-like dispersion is obtained. This dispersion differs from a standard suspension in that it is more viscous than the suspension and is gel-like. Compared with the suspended magnesium alcoholate, the dispersed magnesium alcoholate gel settles down much more slowly and to a far lesser extent.

[0021] As already explained, in step (a) the Mg compound is reacted with a compound Ti compound, having at least a Ti-Cl bond, such as TiCl_4.

[0022] In one embodiment, the magnesium compound is a magnesium alkoxide and the reaction with TiCl₄ is carried out in an inert medium at a molar ratio of Ti/Mg ranging from 0.1 to 10 and preferably in the range 0.2 to 6. In a particular embodiment the Ti/Mg molar ratio ranges 1.5 to 4, and more preferably in the range of 1.75 to 2.75. The reaction temperature may range from 50 to 100°C, preferably from 60 to 90°C. The reaction time in the first stage is 0.5 to 8 hours, preferably 2 to 6 hours.

[0023] The inert suspension media for the abovementioned reactions include aliphatic and cycloaliphatic hydrocarbons such as butane, pentane, hexane, heptane, cyclohexane, isooctane and also aromatic hydrocarbons such as benzene and xylene. Petroleum spirit and hydrogenated diesel oil fractions which have carefully been freed of oxygen, sulfur compounds and moisture can also be used.

[0024] The reaction step (a) may be carried out also in the presence of an electron donor compound. Said electron donor compound can be selected from esters, ethers, amines, silanes and ketones. In particular, the alkyl and aryl esters of mono or polycarboxylic acids such as for example esters of benzoic, phthalic, malonic and succinic acid are preferred. Specific examples of such esters are n-butylphthalate, di-isobutylphthalate, di-n-octylphthalate, diethyl 2,2-diisopropylsuccinate, diethyl 2,2-dicyclohexyl- succinate, ethyl-benzoate and p-ethoxy ethyl-benzoate. Moreover, can be used also the 1,3 diethers of the formula: [0025]

[0026]

[0027] wherein R, R¹, Rⁿ, R^m, R^w and R^v equal or different to each other, are hydrogen or hydrocarbon radicals having from 1 to 18 carbon atoms, and R^VI and R^vn, equal or different from each other, have the same meaning of R-R^v except that they cannot be hydrogen; one or more of the R-R^vn groups can be linked to form a cycle. The 1,3-diethers in which R^VI and R^vn are selected from CrC₄ alkyl radicals are particularly preferred. Also usable are the diolesters donors disclosed in USP7,388,061. Particularly preferred are also the donor mixtures between the succinate esters and the 1,3-diesters above described as disclosed for example in WO2012/139897.

[0028] If used, the electron donor compound is present in molar ratio with respect to the magnesium comprised between 1:4 and 1:20.

[0029] In one embodiment, an electron donor is used in step (a) and the magnesium compound is selected from adducts of formula MgCl₂*nR⁵OH, where n is a number between 0.1 and 6, and R⁵ is a hydrocarbon radical having 1-18 carbon atoms. Preferably, n ranges from 1 to 5 and more preferably from 1.5 to 4.5.

[0030] Adduct of this type are disclosed for example in USP 4,399,054 and us 4,469,648. In a particularly preferred embodiment, the electron donor compound is used together with a MgCl₂*nR⁵OH adduct as Mg compound. In this latter case, it is also preferred to use a Ti/Mg molar ratio higher than 10. Preferably, the Ti compound is TiCl₄ and the reaction is carried out in an excess of liquid TiCl₄ at a temperature ranging from 50 to 150°C.

[0031] The reaction step (a) can be carried out one or more times under the same or different conditions.

[0032] In a further step (b) the product of the reaction step (a) is then contacted with an organo-aluminum compound preferably in such an amount (calculated with reference to the Ti content of the solid catalyst component as obtained by the previous step) to have a Al/Ti ratio of 0.01 to 25 more preferably from 0.05 to 10 and especially from 0.5 to 10. [0033] The organo-aluminum compound may be trialkyl aluminum compound in which the alkyl is a C C^ carbon atoms or an alkyl aluminum chloride in which one or two alkyl groups have been replaced by chlorine groups.

[0034] Preferred tri-alkylaluminum compounds are aluminum trimethyl, triethyl, triisobutyl and tri-n-octyl.

[0035] The alkylaluminum chloride can be selected from the dialkylaluminum monochlorides of the formula R⁶ ₂A1C1 or the alkylaluminum sesquichlorides of the formula R⁶ ₃A1₂C1₃ in which R⁶ can be identical or different alkyl radicals having 1 to 16 carbon atoms. The following may be mentioned as examples: (C₂Hs)₂AlCl, (isobutyl)₂AlCl and (C₂Hs)₃Al₂Cl₃, (ethylaluminum sesquichloride), this latter being preferred. The reaction can be carried out in a stirred vessel at a temperature of from 0°C to 150°C, preferably from 30°C to 100°C for a time ranging from 0.5 to 5 hours.

[0036] In one embodiment, an aluminum alkylchloride compound is used in amounts such that the Al/Ti molar ratio (calculated with reference to the Ti content of the solid catalyst component as obtained by the previous step) is from 0.05 to 1, preferably from 0.1 to 0.5.

[0037] As explained step (b) can be carried out in the presence of small quantities of olefinic monomers thereby producing a pre -polymerized catalyst.

[0038] The amount of monomer used ranges from 0.1 to 100 grams of per gram of solid catalyst component prepared in the one or more step (a) preferably from 0.5 to 50 grams. Preferred olefinic monomers are ethylene, propylene, butene-1 and hexene-1.

[0039] According to a particular embodiment, no monomer is present in step (b) and an aluminum alkyl chloride as previously described is used.

[0040] According to another specific embodiment, the monomer is present and a trialkyl aluminum compound is used.

[0041] In a further embodiment, the product coming from reaction step (a) is first reacted with an aluminum alkyl chloride in the absence of a monomer, and then, the so obtained product is further reacted with a trialkyl aluminum compound in the presence of small amounts of olefinic monomers as described above.

[0042] The product coming from step (b) is then treated in step (c) with a mono or polychlorinated R^Cl compound in a R^l/Al ratio from 0.01 to 10, preferably from 0.01 to 5 more preferably 0.1 to 3 and especially from 0.5 to 3 where R¹ is hydrogen or a Ci-C2o hydrocarbon group.

[0043] In a preferred embodiment the RZ-CI compound is a chlorinated hydrocarbon chosen among monochlorinated hydrocarbons. More preferably, it is chosen among monochlorinated alkyls having from 1 to 10 carbon atoms.

[0044] Non limiting exemplary compounds R^Cl are hydrogen chloride, propylchloride, i- propylchloride, butylchloride, s-butylchloride, t-butylchloride 2-chlorobutane, cyclopentylchloride, cyclohexylchloride, 1,2-dichloroethane, 1,6-dichlorohexane, Among them, particularly preferred are butyl chloride, i-propylchloride, 2-chlorobutane and cyclopentylchloride. Preferably, the component R^Cl is used in such amounts to give a molar ratio between with the Ti atoms contained in the solid coming from step (b) of higher than 2.5, preferably higher than 3 and more preferably higher than 3.5.

[0045] The reaction step (c) is preferably carried out in the presence of a suitable dispersion medium such as an inert liquid hydrocarbon. In an embodiment the so obtained slurry constitutes the final catalyst that can be shipped in this form.

[0046] In an alternative embodiment, the solid catalyst coming from step (c) is then recovered and isolated from the slurry using conventional techniques, such as filtration, and subsequently dried.

[0047] For storage or shipment the so obtained dried catalysts can be suspended in liquid hydrocarbons such as hexane, or more viscous substances which preserve them from contact with water.

[0048] As explained above and illustrated in the working examples the so obtained catalysts when is put in contact with water releases no or very limited amount of flammable gases. This allows the catalyst to be packed and shipped with a low risk category. Moreover, it is worth noting that the reduction of flammable gas emission is obtained maintaining the catalyst performances in terms of activity and hydrogen response at substantially the same level so that catalyst users do not need to change operative parameters when using the catalyst.

[0049] The so obtained catalyst component can be used together with an organo aluminum compound (B) in the ethylene polymerization.

[0050] The organoaluminum compound (B) is preferably selected from the trialkyl aluminum compounds such as for example trimethylaluminum (TMA), triethylaluminum (TEAL), triisobutylaluminum (TIBA), tri-n-butylaluminum, tri n-hexylaluminum, tri-n-octylaluminum, triisoprenylaluminum. Also alkylaluminum halides and in particular alkylaluminum chlorides such as diethylaluminum chloride (DEAC), diisobutylalumunum chloride, Al-sesquichloride and dimethylaluminum chloride (DMAC) can be used in mixture with said trialuminum alkyls. Use of TEAL and TIBA is preferred.

[0051] The catalysts systems of the disclosure are particularly suited for liquid phase polymerization process. In fact, the small average particle size, such as less than 30μιη, preferably ranging from 7 to 15 μιη, are particularly suited for slurry polymerization in an inert medium, which can be carried out continuously in stirred tank reactors or in loop reactors. In a preferred embodiment the ethylene polymerization process is carried out in two or more cascade loop or stirred tank reactors producing polymers with different molecular weight and/or different composition in each reactor, thereby showing as a whole a broad molecular weight distribution.

[0052] In addition to the ethylene homo and copolymers mentioned above, the catalysts of the present disclsoure are also suitable for preparing very-low-density and ultra-low-density polyethylenes (VLDPE and ULDPE, having a density lower than 0.920g/cm 3 to 0.880 g/cm 3 ) consisting of copolymers of ethylene with one or more alpha-olefins having from 3 to 12 carbon atoms, having a mole content of units derived from ethylene of higher than 80%; elastomeric copolymers of ethylene and propylene and elastomeric terpolymers of ethylene and propylene with smaller proportions of a diene having a content by weight of units derived from ethylene of between about 30 and 70%.

EXAMPLES

[0053] The results for the elemental composition of the catalysts described reported in the examples were obtained by the following analytical methods:

Ti: photometrically via the peroxide complex

Mg, CI: titrimetrically by customary methods

MFRs/igo: mass flow rate (melt index) in accordance with IS01133, nominal load of 5 kg and test temperature = 190°C

FRR2L6/5: flow rate ratio; quotient of MFR21.6g/190° and MFR5g/190° Bulk density: in accordance with DIN EN ISO 60

dso (mean particle diameter): in accordance with DIN 53477 and DIN66144

M_w/M_n (polydispersity): Measure of the width of the molar mass distribution (M_w = weight average, M_n = number average), determined by the GPC method in accordance with

DIN55672. The measurements were carried out at 135°C using trichlorobenzene as solvent.

Reaction with Water test

This test is performed at ambient temperature (20°C) and atmospheric pressure in an inert gas atmosphere inside the apparatus consisting of a conical flask equipped with a dropping funnel and a syringe at a gas outlet junction at the upper part of the conical flask Water (100 ml) is put into the dropping funnel and the catalyst sample is placed in a conical flask. The tap of the dropping funnel is opened to let the water into the conical flask and a stop watch is started. The volume of gas evolved is measured by a syringe.

Example 1

4] Preparation of the solid catalyst component

All catalyst preparation steps are performed under inert gas atmosphere as this type of catalysts are very air and moisture sensitive.

A catalyst component was prepared according to the procedure disclosed in example 2 of EP1507805. A dried catalyst sample is re-suspended in diesel oil (hydrogenated petroleum fraction having a boiling range from 140 to 170°C), the stirred slurry was then treated with 1- butyl chloride in a ratio of 0.002 mol per g of solid catalyst at 75°C for 2 hours. The resulting 1 -butyl chloride treated catalyst sample was filtered off and dried by nitrogen purging.

The so obtained catalyst was subject to the reaction with water test described in the characterization section. Results are reported in table 1.

Ethylene polymerization in suspension:

The polymerization experiments were carried out batchwise in a 1500cm³ reactor. This reactor was equipped with an impeller stirrer. The temperature in the reactor was measured and automatically kept constant. The polymerization temperature was 85 +1 °C.

The polymerization reaction was carried out in the following way: 800 cm of diesel oil (hydrogenated petroleum fraction having a boiling range from 140 to 170°C) were placed in a 1.5 dm reactor. The reactor was then heated to 85°C and, under a blanket of nitrogen, 2 mmol of triethylaluminum as cocatalyst and subsequently the catalyst prepared as described in Example 1 a in an amount corresponding to 0.05 mmol of titanium, as a suspension diluted with diesel oil, were introduced into the reactor. The reactor was then pressurized with 3.15 bar of hydrogen and 3.85 bar of ethylene. The total pressure of 7 bar was kept constant during the polymerization time of 2 hours by replacing the ethylene which had been consumed. The polymerization was stopped by shutting off the ethylene feed and venting of the gases. The polymer powder was separated off from the dispersion medium by filtration and drying.

The results of the polymerizations are shown in Table 1.

Example 2 (Comparative)

[0055] Example 1 was repeated omitting the step of reaction with the 1 -butyl chloride.

[0056] The catalyst was subject to the water reaction test and to ethylene polymerization procedure as in example 1. Results are shown in table 1.

Example 3

[0057] Example 1 was repeated using dry hydrogen chloride gas as treatment agent purged slowly through the catalyst slurry applying a temperature of 50°C.

[0058] The catalyst was subject to the water reaction test and to ethylene polymerization procedure as in example 1. Results are shown in table 1. TABLE 1

Claims

CLAIMS What is claimed is:

1. A solid catalyst component comprising the product of a process comprising

(a) reacting at a temperature ranging from 0 to 150°C a Mg based compound of formula (MgCl_mX₂-m)'nLB, in which m ranges from 0 to 2, n ranges from 0 to 6, X is, independently R, OR, -OCOR or -OC(0)-OR group, in which R is a C C₂o hydrocarbon group, and LB is a Lewis base, with a Ti compound, having at least a Ti-Cl bond, in an amount such that the Ti/Mg molar ratio is greater than 0.1 optionally in the presence of an electron donor compound thereby obtaining a catalyst precursor;

(b) reacting the product coming from the preceding step with an organoaluminum compound in such an amount to have a Al/Ti ratio of 0.01 to 50 optionally in the presence of an amount of olefin monomer able to produce from 0.1 to 50gr of polymer per gram of catalyst precursor; optionally followed by one or more washing steps;

(c) treating the catalyst precursor coming from step (b) with a mono or polychlorinated R^Cl compound in a R^l/Al ratio from 0.01 to 10 where R¹ is hydrogen or a Ci-C₂o hydrocarbon group and

(d) isolating and recovering the solid catalyst component.

2. The solid catalyst component of claim 1 in which the Mg compound is a magnesium alcoholate of formula Mg(OR 2 )(OR 3 ) compound, in which R 2 and R 3 are identical or different and are each an alkyl radical having 1 to 10 carbon atoms.

3. The solid catalyst component of claim 2 in which R 2 and R 3 are C Ci-alkyl radical.

4. The solid catalyst component of claim 2 in which the magnesium alcoholate is used as a gel dispersion.

5. The solid catalyst component of claim 1 in which the Ti compound is TiCl₄.

6. The solid catalyst component of claim 2 in which the molar ratio of Ti/Mg ranges from 0.2 to 6.

7. The solid catalyst component of claim 1 in which in step (b) the product of the reaction step (a) is contacted with an organo aluminum compound in such an amount to have a Al/Ti ratio, referred to the Ti content of the solid catalyst component as obtained by the previous step, ranging from 0.05 to 10.

8. The solid catalyst component of claim 7 in which the organoaluminum compound is chosen from trialkyl aluminum compound in which the alkyl is a CrC₁₆ carbon atoms or an alkyl aluminum chloride in which one or two alkyl groups are replaced by chlorine groups.

9. The solid catalyst component of claim 8 in which the organoaluminum compound is chosen from aluminum trimethyl, triethyl, triisobutyl and tri-n-octyl, (C₂Hs)₂AlCl, (isobutyl)₂AlCl and

10. The solid catalyst component of claim 1 in which in step (c) the RZ-CI compound is a chlorinated hydrocarbon chosen among monochlorinated hydrocarbons.

11. The solid catalyst component of claim 1 in which the R^Cl compound is used in a R^l/Al ratio from 0.01 to 5.

12. The solid catalyst component of claim 11 in which the R^Cl compound is used in a R^l/Al ratio from 0.1 to 3.

13. The solid catalyst component of claim 1 in which the R^Cl compound is selected from hydrogen chloride, propylchloride, i-propylchloride, butylchloride, s-butylchloride, t-butylchloride, 2-chlorobutane, cyclopentylchloride, cyclohexylchloride, 1,2-dichloroethane, 1,6- dichlorohexane.

14. The solid catalyst component of claim 1 in which step (b) is carried out in the presence of small quantities of olefinic monomers thereby producing a pre-polymerized catalyst.

15. The solid catalyst component of claim 14 in which the amount of monomer ranges from 0.1 to 100 grams of per gram of solid catalyst component prepared in step (a).